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Originally appeared in: PROCESS OPTIMIZATION

April 2006, pgs 83-91.


Used with permission.

Prevent system hydrate formation


during sudden depressurization
Using this technique can help size gas plant inhibitor packages
B. ASADI ZEYDABADI and M. HAGHSHENAS, Namvaran Management and
Engineering, Tehran, Iran; S. ROSHANI, Petrochemical Industries Design & Engineering
Co., PIDEC, Shiraz, Iran; and M. MOSHFEGHIAN, Shiraz University, Shiraz, Iran

A
hydrate is a physical combination of water (H2O) and body-centered cubic called Structure I. Larger molecules pro-
other small molecules producing a solid, which has an pane (C3H8), isobutane (iso-C4H10) and n-butane (n-C4H10)
ice-like appearance but possesses a different molecular form a diamond-lattice called Structure II. Molecules larger than
structure. Formation in gas and/or natural gas liquid (NGL) n-C4H10 do not form hydrates as they are too large to stabilize
systems can plug pipelines, equipment and instruments, and the lattice.1
restrict or interrupt flows. There are three crystalline structures Gas composition determines structure type and mixed gases
for hydrates. In each, H2O moleculeshost moleculesbuild will typically form Structure II lattices. Limiting hydrate num-
the lattice, and hydrocarbons, nitrogen (N2), xenon (Xe), argon bers (the ratio of H2O molecules to molecules of included gas-
(Ar), carbon dioxide (CO2) and hydrogen sulfide (H2S)guest eous component) are calculated using gas molecule sizes and
moleculesoccupy the cavities. Smaller molecules such as cavity sizes in a H2O lattice. The structure type does not affect
methane (CH 4), ethane (C 2H6), CO2 and H 2S stabilize the appearance, properties or problems caused by the hydrate; it

To HP are header
RC
FT To HP are header
MeOH from distribution header
To gas sweetening unit (train 1)
To gas sweetening
FT To gas sweetening unit (train 2) unit (train 2)
HIPs system
To gas sweetening
PS PC unit (train 1)

HIPs valves
Compressed gas from compression units

M Inlet gas Inlet gas


LC LC
separator (A) separator (B)
Slug catcher
M LC
Gas/cond. from M LSLL
offshore pipeline

Pig receiver
To/from fuel FC To condensate stabilization
gas heater MP separator (train 2)

FC To condensate stabilization
HS MP separator (train 1)

NNF To burn pit

FIG. 1 A typical gas and condensate reception/separation unit PFD.

HYDROCARBONPROCESSING APRIL 2006 1


I
PROCESS OPTIMIZATION

PB O
C DZL O To HP are header
N2 from distribution header
C
3 Open To HP are header
DZSO
2 Clo
XZL se
(2) d
ESD
XZL Set press: Set press:
(1) 78 barg 78 barg S.C.
DY DZSC
S
XZSC DY PSV PSV
S RO
IAS XZSO (1)
RO
MeOH from (2)
IAS
Vent Vent EDPV
distribution header
To gas
sweetening
XV
train 1,2

ESDV
(2) From inlet gas
separator (B)
ESDV
(1)

Inlet gas
From slug separator (A)
catcher

FIG. 2 A typical pipeline between slug catcher and inlet gas separator P&ID.

does, however, have a significant effect on the pressure and tem- Fundamental equations. For a gas system, hydrate and pure
perature at which hydrates form. Also Structure II hydrates are H2O coexist with each other at equilibrium. These equations deter-
more stable than Structure I. Structure H hydrates are a double mine the equilibrium temperature when H2O is present:6,7,18
hydrate that requires two kinds of molecules to be stabilized:

a small molecule like Xe, Ar or H2S and a larger molecule like
methylcyclohexane.2,3
To
(
w RTR hw RT 2 dT + ( w RTo ) P i ln 1 + C i j
TR
)
i j
2
Natural gas mixtures that have H2S present
RTR
To result in a substan-
whaRT (
To
RT pressure.
T oT h
) (((
(RTw 2RT
2
dT)+Pw(RT

))
(( RT
To
lnoT)1ToPo+h

(
w CRT i ln )
f j2dT
11+ln+x(wC i wj0f RT ) Pxw
o ln = 0 i ln (1)1 + C i j

) oT)R)PP h ( ) 1++
2
wtemperature dT o +w
C= j (1)
w RTR TR hw RT j (C
tially warmer hydrate formation TRat w RT wgiven R TR hw RT
2 dTo + w RT
RT
w w= i hwwR + oT C jp
RT ij ln + i j f fj RT oln)lnPxxww= 0 (1)
1 +
R wR
dT
h+ i RT
i, w dT
i
i ln
dT i wj j i= 0 i ln(1) j Ci j
CO2, in general, has a much smaller impact and often reduces T the TR R
w
i
j j
R
i i j
hydrate formation temperature at fixed pressure To for a hydrocarbon
To To
hwp ,=w =haw++b(TTooCTpR, w) dT
hhw ++ TRT

hw = hw + hw C = hwdT + To C p , w dT C (2)
gas mixture.4,5 TRhh w == C p , w dT hw = hw + TR C p , w dT
(2) (2)

o
TR C p , w dT
p,w (2)
w w
Hydrate and hydrate formation processes are well known, TR and TR

+ b C p, wT=)gas
(Tnatural a + b (Todesal- T ) C p , w = a + b (To TR ) (3)
this phenomenon is used as a means toastore
C p ,w = CoCp , w R==aa++and bb(T(To TTRR ) ) b (To exp
(3)
0 TR[) (r ) kT ]r dr
(3)
i j (Tp )

inize seawater. However, in the gas industry, hydrate formation in
p , w o R C C , w== 4a +kT 2 (3)
pipelines causes operational problems which ought to be Tconsid- The Langmuir constants in Eq. 1 can be calculated: 8
2
Ci j (T ) = 4 kT
ered during basic design. Consequently,
C
additives (

)
RT
T exp
CCi j (0T(glycol
4R[kT
= like
) = 4 kTkT (
o
methanol) kT

w] r [
hexpRT (
2 (rdT
TR 0 exp[ (r ) kT ] r 2dr
r dr
2
)kT
C
)
+j w(]TrRT)
2
2=drw4RRT
kT
To
oT) P
hexp(
w RT [
i )
ln(rdT1) +kT + (]rC2i wdr f RT o )lnPxw

(4) = 0 i (4)ln
(1) 1 + Ci j f

i j T ) = 4(TEG) 0 0 oexp r [ (r )CkT i j (T ]r) =dr4HkTR 100 exp [ (r ) kTj ]r 2 dr
w j j
(MeOH), ethylene glycol (EG) and triethylene
i j i
i1 i (4)
(4)
j
ln a =
their mixtures in hydrate inhibitor packagesare injected into T To
w
To nR o T
pipelines preventing gas hydrate formation. Due
H
hw to hw +H 1C p ,1w dT
= depressurization
1a =1HTR 1 1 hEq.
In w = 4,h(r)
w+H 1Cspherically
isT the

p ,1w dT symmetric cell potential which (2)
ln Hsalts 1and ln
1 can be expressed a = H 1 1 of the radius, coordination
(5)
R
ln aHw2=
in a natural gas plant, produced Onaturally a wcontains
ln = w asa function (5) number (5)
nRCln awwT= nR
T(NaCl),
T To ln a w =potential nR Tparameters.To 8 The gas phase fugacity, f , can (5)
electrolyte solutions such as sodium chloride = oa + bnR (
potassium
nR T T T T T T) and C
Kihara = a + b
nR( T T T T) (3)
w ) [A +
o
o R o
B ) x w ] of state.
i
= (1 a xreliable 2( Aequation
p ,w o p , w o R 2
chloride (KCl) and calcium chloride (CaCl2). These act as inhibitors ln a w x wusing
be calculated PVT 9

but are not used individually as hydrate depressive media. To suppress hydrate temperature at a given pressure, alcohol
( ) 2 [ A + and
2
2r()C ar))w2x=dr ] (1 xexp )22[[Ain ( A Br)2xdr ] (6) The calcula-
[A+(r2)( AkT]for
Being able to calculate adequate = C(1ln
ln a w x wamounts ( a w)of) [
2xinhibitors
=+kT 1(Axexp to) 2[x ] ( AkTln
(BT]
glycols xare=kT
usually wused + 2inhibition wpackages. (6)
be injected into pipelines for flare networks
ln
i jln aTx
a w = 4
x
iswwimportant
w = (
xww = (10from
A 21 x wB )
xww ) [A +tion
A
w
+ 2 ( A
2( Ato
iln
j B ) x w4]
Ba)wxwwx]w =hydrate
w
10 x w )temperature
(2063 B ) xawgas ] hydrocarbon(4) (6)
(6)
Hsuppress plus
an economical viewpoint. Determining the type and optimum H2O is:1,10,11,14 =
amount of inhibitor is the first step in designing such packages. nR 1 + 2 P + 3 ln P
H H
2063 H 2063 1 1 H H 2063 1 1
Thus, there is an incentive to demonstrate
= aHH
alnsimple w=
= methodology 2063
2063 lnaH w
= 2063 (7) (7)
(5)
(7)
nR its
to select inhibitor type, calculate + 2 P nR+ =ln
1 effectiveness +P 2find
nR
1 and PT + anT 3oln P nR = 1 nR + 2 P T + T3o ln P (7)
nR + P
nR 3 1 1 + 2 2 P + 3 3 ln P + ln P nR 1 + 2 P + 3 ln P
economic flowrate.
ln a w = mk mk ln a w , k ( )
I
2 APRIL 2006 HYDROCARBONPROCESSING
ln a w x w = (1 x w ) [A + 2( Aln
2
Ba)wx wx]w k= (1 x w ) [A + 2( A B ) x w ]
2
(6)
ln a = m m ln a
(
) ln a = m m ( 1

ln a ) (8)
To
To
hw = hw + C p , w dT hw = hw + C p , w dT (2)
TR
w RTR (hw RT 2 )dT

w RTwR o (hw RTi )dT + ( wi j RT
T To
( )
RT
To
P 2ln 1 +
C f
j o ) P w
ln x 0 1 + Ci
R
+ = i ln(1)
( R T PROCESS
) OPTIMIZATION
C p , w = a + b (To TR ) C = a + b T T
TR
p ,w o R i j i (3) j


hwR+T( (w ) )
To To TT
hw = hw + C p , w dT whwRT + (+2(wRT ) P i lni 1ln(2)
w oRTo ) P
+
1j+ i j C
2
h ChpRT dT C f
oo 2
, w dT

w= RRT RT dT
i j (T r)2=dr 4 kT R RRexp[ (r ) kT ]r dr
TR w
Ci j (T ) = 4 kT exp[ (r )CkT ] T T
i i (4) j
0
C p , w = a + b (To TR )
300 0 250
C p , w = a + Tbo (TToo TR ) EG
(3)
EG hw=hwh=w+hw + C w dT
p ,C p , w dT MeOH
MeOH T T
H 1 1 H R 1 R 1
lnCa w (=T) = 4 kT exp
ln a w = 2 (5)
nR T 0To [
(rCC)240 ]r, wa==+nR
ip ,j w(Tp )
kT C= 4ab(+TkT
dr
0 o)TR[) (r ) kT ]r dr
boT(TTo TRexp (4)
290 2
ij

2 [ r )B]kT

(aTi )j (=Tx4)==4kT A1+[2(r(
)A(kT r) x2 ]dr

)wxaww ]w= (1HkT0xw1)0[exp


H 12 1 Ci j C exp
w]
r 2 dr
ln alnw axww==(1 xw ) [A + 2( Aln
280 230

Temperature, K
Temperature, K

Bln (6) (5)


nR T To nR T To
HH1 11 1
270
H 2063 ln aln
H
220w =a w = 2063
Aln=aBw) xxw+nR
ln=a w x w = (1 x w ) [A + 2(nR ] nR T TTo 2To (7) (6)
P ) P[A + 2( A B ) x w ]
2
nR 1 + 2 P + 3 ln P 1 w=2
(1+x3wln

260 210
ln alnw axww =x w(1=(1x w)x w[A + 2( A B ) x ]
2063 ) [A + 2( A Bw) x w ]
2 2
H 2063 H
= = (7)
ln a w = (1mk m 1(m+k 2mPk+)ln 3aln
k )ln a w , k w =
nR + 2 P + 3 ln P ln anR
w , kP
250 200
(8)
k k
0 10 20 30 40 50 60 HH 0 2063
10 206320 30 40 50 60
Wt.% 1 H = = 0 I 1 Wt.%
H I nR =nR 1 +1 2+P 2+P 3+ln 3Pln P
= 0
nR 4 1 +Gas P + 1 ln
0 mixture P (9)
1 +comparison
((hhw RT )
2 FIG. (
3 Gas mixture
o (h
To
) i 2 ) dT
hydrate-formation
2ln1 +
++
nR
temperature
(EGCatwii jj79
ln P
)PPlnw(upstream
a = (
+ m ln
m P

)
i lnk 11+k+ CCwi, kj ff j lnalnlnw inxx=wthe
ln a FIG.
=k=00(presence mk )oflnMeOH
hydrate-formation temperature comparison
a w , k and EG at 1.4 bara (downstream (8)
w RT )
dT RT P C f ln xw
x 0 1(1)
+ =

0
2 RTwin
w ( R the ) RT RT mk (1)
ToR ( Phw )
dT + w RT
Topresence ofMeOH
i ln
1and ( o
f jj bara ) wk=0i ln(1)
w RTRof TR
EDPV). w i
i
RT dT


+ j
j
w RT

o i j i j j of EDPV).
w (1)
H i
1 j
dT )dT hRww+ToTRo( C p , wi dTi )dT
I
hw+ (= RT To)Phw RT ln 1 + I 1
To
(Cwi jlnRT f j o ) Pln =x 1 + C i j flnj aH (
=m0a(m
k+)m lnk a)ln
2
Chwp , w RT w = 0i 0ln(1)
2
RT lnln x=w=ln
=a=w 0 (1)
C p , w dT where: hw = hw + TR C p , w dT
w j anR = ln a (2)
+
(2) ln
w , mix . 1 +i 0wP, al+ 1 lnwjP, el a

nR
w , mix .
1k +
k
k w ,m
P
k(2)
al
(2)
+ ln
ka w , k
w , el
P (10)
(9)
0 1
TRT w,al is obtained by Eq. 6 and lnaw,el by Eq. 8.
To (hw RT ) dT
2 ) P ln
(ThRw) RT 2 )
aw is H2O activity
w+ (RT
( ) ) + (Cw RT o ln x= 0i (3)
1 + where f jlna
ln x w= 0I 1(3)
o

R+ C ij H I(1)

o

CTp R, w)dT H dT C
= a
bRT T P T ln 1 + f (1)
H hydrate 0 0formation
1
=haw ++b (TTTformation TpR, w) i (2)
(3)

hCw pp=,,wis
whydrate w R C R dT enthalpy

o i i j j w
i j
To find = = (2)
(3) enthalpy, a method that does not
o j nR nRmixture 1 + H P + H ln P
n is the hydrate R
number H H consider
2 1 + P +
composition ln P by averaging formation enthalpy in
ln2a w , mix .= ln a(3)
0
ln 0 1
1+ ln a plus H O and alcohol plus H O
T ) w , al+ ln aseparate, elH ln mixtures
a a (10)
o
CR p [, wdT
exp (rC) RCis the
kThpw,]w=
( =
r)the
2 auniversal
dr +
b (T
To gas constant
hw + o CRp , w dT
T ) [ ( ) ] 2 H nR al nR (4)(2)
w
el should= be considered. w nR
, mix . =
of
electrolytes
nR
(3)
w (2)
, al w , el 2 2

kT 0 exp[ (r ) kT ]r dr
al el
0 exp[ (r ) kT
Ci jo(T])r= 4dr

T T
is = 24
hydratekT T exp
temperature r kT
in the r 2 dr
absence = of inhibitors (4) (4) 6 The harmonic average technique (11)
can be
i j
nR H
used forthis purpose: (4)H
R
0
(pure H2O) 0 nR H H +
T ) C = a + b ( T T ) + nR nR (3)
o expR[ (r ) T nR nR (3) ln a ln a = ln = a ln a + ln ela w , ela w , el
w , al + ln
10 1 CiPredicting ]r dr suppressed
ispthe
, w2 suppressed
j (T ) = 4 kT
kT

o temperature.
exp[hydrate
R
(r ) kT ] r 2
dr
2

alH (4)
Hel w , mix .

w , mix .
al
H w
(4)
, al
H
1 1 H 01 1 temperature in the presence of 2 (5)
ln a w glycols, 1 1 and mixtures must
= H electrolytes H nR al (5) nR el
(5) H nR
al (5) el nR
T To alcohol,
ln a w = nR T To be
= outlined.
= (11)
T To
[ ( C ) (
i jkT ] r dr
T ) =2 4To
nR kT T exp
T [ (r ) kT ] r 2
dr nR H H (4)
1 0 1 solution, H OHactivity
exp r Alcohol. solve
Eq. 5,
o when hydrates coexist with
2 +
an alcohol(4) nR H H
1 1 be found by the Margules
0 H 2H +H H
ln a w = 2 may X = nRequation: al (5) nR el X2=2nR al (5) nR (12)
T2 o nR T T2o 1 2 H H 1 nR nR nR
al 2 al nR el elel
x w ) 2 [A + 2( Aln aBw) xxww] =H = =
aB ) xxw ]= ((11 xx1w ))2 1[[A A+ 2( A B ) x w ] (6)
x1w ) 1[A+ 2( A lnln + 2( A B ) x w ] (6) nR nR H H + (6) (6)
H (5)H
aww = w w (5) where nR nR
and + must be calculated using
nR T T al al nR nR el el
T 2 To
x w ) [ A + 2( A The expressionof DH/nR o
2 (6)
lnaBw) xxww]= (1 x w ) [A + 2( A B ) x w ]
2 for alcohol is:1 2 (6)
X = X = (12)
63 H 2063 1 2(7) Eqs. 7 and 9, respectively. 1 2(7)
63 H = 2063
+ 3 ln P nR = + P + 2ln P (7) (7)
+xw 3) ln[AP+ 2( A nRaBw )xx11ww+]= 22(1P+xw 33) ln[AP+ 2( A B ) x w ]
ln 2 2 (6)
2
(6)
63 H 2063 Inhibition X =X =package sizing procedure. In hydrocarbon
= (7) 1 1 2 (7)
+ 3 ln P The parameters
nR 1 + 2 P + 3 ln P in the above equation are also valid for MeOH, processing industries 2(HPIs), an important aspect in basic engi-

EG and glycerol. 6 neering is to perform safety and risk analyses.15 Fire, mal-opera-
H 2063
mk)ln a w, k Electrolytes.
063
a = +(m
=
+kk ))ln
(7)
Pm+k )ln

lnnR Hm 2O
activity
ln a in a hydrate coexisting with(8) (7)
an tion, equipment failure (8)and other such events are summarized in
a w , k ln
3 ln Paqueous a ww = kk1 (mk2k Pmmixtures
electrolyte 3 ln a wwP,,kkis expressed:12 (8)
a report after a hazard(8) and operational study (HAZOP), and/or
safety meetings handled by experienced engineers, are performed.
1 )ln a lnHa w = (
m00k I m1 k )ln a w , k

I 1
1
m
(9)(8) The primary goal is (9) (8)pinpoint where and how dangerous situ-
to
k w,k H = (9)
1 ln P nR = 1 +k 0 P + 1 ln P ations may arise and, (9)secondly, to propose the best possible pre-
1 ln P nR 1 + P + ln P
mk )ln a w , k Hln=a w =w,k k(0mIk m11,14 k )ln a w , k
0 1 13
where lna is calculated using a developed software model. ventive actions.

1 1
(8)
DH/nR is calculated: (9)(8) One consideration (9)is to perform a study on gas vapor buildup
1 ln P nR 1 + 0 P + 1 ln P
1 in process equipment. To design an effective and reliable safety
al + ln a w , el
1
+ ln a lnHa w=, mix . = lna0 wI, al + ln a w , el
(10)
(10) instrumented system (10)
(9) (SIS), many standards such as API must
al w , el ln a w , mix . = ln a w , al + ln a w , el (9) (10)
1 ln P nR 1 + 0 P + 1 ln P be considered. 16 During abrupt pipeline or equipment depres-
surization, contents are normally released to the atmosphere or
al + ln a w , el ln a w , mix . = ln a w , al + ln a w , el (10) (10)
H Electrolytes and alcohol mixtures. H O activity in the case of through a flare network. Clogging emergency depressurizing
H H H 2
hydrates 2
H
coexisting
H
with
a electrolytes and alcohol mixture is: 6,18 valves (EDPVs), pressure safety valves (PSVs) and flare header
nR el Hln a2w, mixnR nR+lnel a
nR el a w , el . = lnala w ,nR (11) (10)
w , al +ln H = nR al el (10) (11)
al w , el
(11)
H H
H nR = HH HH
nR
2
H
+ H
(11) HYDROCARBONPROCESSING APRIL 2006 3
I
nR

nR el H nR nR nR + nR
PROCESS OPTIMIZATION

TABLE 1. Raw natural TABLE 3. P-T history calculated for upstream and downstream of EDPV and also
gas and its composition predicted hydrate formation temperature at each step of depressurization process
used in this study
Step Time, h Upstream Upstream Upstream2 Downstream Downstream Downstream2
Component Mole% pres., bara temp., K hydrate pres., bara temp., K hydrate
temp., K temp., K
N2 3.12
1 0.000 79.0011 287.2 290.4 1.40 236.2 236.5
CO2 1.85
2 0.375 24.18 228.7 281.2 1.32 206.4 233.3
H2S 0.50
3 0.500 16.97 216.3 277.6 1.31 200.1 231.4
CH4 86.08
4 0.750 8.47 196.0 263.9 1.30 187.8 227.6
C2H6 5.45
5 1.125 3.03 173.4 237.7 1.30 171.2 223.1
C3H8 1.79
6 1.375 1.57 162.7 224.3 1.30 162.3 221.2
Iso-C4H10 0.30
1 Design pressure of inlet gas separator. Operating pressure and temperature are 71.5 barg and 287.2 K, respectively.
N-C4H10 0.45 2 Hydrate temperatures computed by created software and counter-checked with industry-available software.

Iso-C5H12 0.13 TABLE 4. Released gas analysis at each step of P-T history of depressurization
N-C5H12 0.12 process
Light Aromatics 0.01
+ 0.20 Mole fraction
C6
Component Step 1 Step 2 Step 3 Step 4 Step 5 Step 6
TABLE 2. The blowdown N2 0.0312 0.0319 0.0321 0.0324 0.0325 0.0322
rates calculated for EDPV CO2 0.0185 0.0185 0.0185 0.0184 0.0182 0.0183
based on API RP 521 H2S 0.0050 0.0048 0.0046 0.0042 0.0036 0.0034

Step Time, h Vent rate, Vent rate, C1 0.8608 0.8742 0.8801 0.8898 0.8998 0.9030
kg/h m3/h C2 0.0545 0.0527 0.0512 0.0476 0.0423 0.0405
1 0.000 22,209.7 278.9 C3 0.0179 0.0141 0.0113 0.0068 0.0034 0.0024
0.125 18,719.1 275.2 iC4 0.0030 0.0016 0.0010 0.0004 0.0001 0.0001
2 0.375 11,205.1 268.0 n-C4 0.0045 0.0018 0.0010 0.0003 0.0001 0.0001
0.500 6,132.5 263.0
iC5 0.0013 0.0002 0.0001 0.0001 0.0000 0.0000
3 0.625 4,345.4 261.0
0.750 3,095.9 258.6 n-C5 0.0012 0.0001 0.0001 0.0000 0.0000 0.0000

4 0.875 2,218.2 256 Lt. Arom. 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
1.125 1,405.5 252.3 C6+ 0.0020 0.0001 0.0000 0.0000 0.0000 0.0000
5 1.375 731.8 246.3 Total 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000

inlets with hydrates that are formed due to pressure reduction can down under fault conditions. In gas industries, due to H2O coex-
impose grave and perilous operating problems. isting with gas and condensate hydrocarbons, the probability
Injecting an inhibitor into the system is an accepted industry of hydrate formation in process pipelines is high during emer-
practice simplifying the pressure reduction process and preventing gency depressurization. Therefore, all pipelines between the pig
hydrate formation. To demonstrate sizing procedures for inhibi- receiver, slug catcher and inlet gas separators (Fig. 1) must be well
tion packages, a gas and condensate reception/separation unit for appointed with an effective and reliable ESD system.
an onshore refinery is used as an example. All pipelines connected to an ESD valve, which is equipped
Referring to the process flow diagram (PFD) in Fig. 1, the with a hydrate inhibitor injection system, are part of the ESD
incoming feed facilities are designed to receive hydrocarbon gas system. A piping and instrument diagram (P&ID) shows details
and liquid from an offshore pipeline. Feed is then separated into between the slug catcher and one of the inlet gas separators (Fig.
gas and liquid streams so that it can be further processed in the gas 2). The ESD valve is designed to depressurize and protect the
sweetening and condensate stabilization units. It also provides the inlet gas separator. Process thermodynamics manifests while a
ability to handle random slugs formed during normal operation pressurized system is relieving its contents as gas, thus the sys-
and those generated by periodic pigging operations. tems pressure and temperature (P-T) changes with respect to
The hydrocarbon fluid from the offshore pipeline flows into time. Therefore, P-T history must be acknowledged and realized
the slug catcher where the hydrocarbon gas and liquid are coarsely before a hydrate formation calculation at any given pressure can
separated. The gas flows under control via the inlet gas separator be done. Table 1 shows gas composition used and the C6+ fraction
to the gas sweetening units. The inlet gas separator is located is characterized as n-decane and the light aromatics as benzene.
downstream of the slug catcher and is designed to remove liq-
uid carry-over from the coarse gas liquid separation in the slug P-T history. When metal is exposed to fire on one side with
catcher. The liquid flows under level control to the condensate vapor/liquid on the other, the metal temperature may reach a
stabilization units. level at which a stress rupture may occur; even though the pres-
To prevent a worst-case scenario for a safety integrity level sure within the vessel does not exceed the allowable over-pressure
(SIL), the plant will be provided with an emergency shutdown (110% of the design pressure). It is on this basis that an emergency
(ESD) system. This ensures safe isolation and equipment shut- vapor depressurizing (blowdown) system is used.
4
I APRIL 2006 HYDROCARBONPROCESSING
PROCESS OPTIMIZATION

TABLE 5A. Upstream inhibitor flowrate calculation TABLE 5B. Downstream inhibitor flowrate
at step 1 of EDPV depressurization process calculation at step 1 of EDPV depressurization process
(P = 79 bara) (P = 1.4 bara)
Inhibitor1 Hydrate2 Depression3 Flowrate,4 kg/h Inhibitor1 Hydrate2 Depression3 Flowrate,4 kg/h
wt% temp., K value, K 100%5 96%5 90%5 wt% temp., K value, K 100%5 96%5 90%5

0 290.4 3.2
0 236.5
0.3

10 284.5 2.7 0.11 0.12 0.13
10 233.3 2.9 0.11 0.12 0.13

20 278.6 8.6 0.25 0.26 0.29
20 229.4 6.8 0.25 0.26 0.29

30 272.5 14.7 0.43 0.45 0.50
30 224.8 11.4 0.43 0.45 0.50

40 266.0 21.2 0.67 0.71 0.80
40 219.3 16.9 0.67 0.71 0.80

50 258.9 28.3 1.00 1.09 1.25
50 212.7 23.5 1.00 1.09 1.25

60 250.9 36.3 1.50 1.67 2.00
60 205.0 31.2 1.50 1.67 2.00
1  eOH is selected as inhibitor in inhibition package. Also, wt% in this column shows inhibitor
M 1  eOH is selected as inhibitor in inhibition package. Also, wt% in this column shows inhibitor
M
wt% in the condensed liquid H2O phase in the pipeline. wt% in the condensed liquid H2O phase in the pipeline.
2 Hydrate temperatures are computed by created software and counter-checked by indus- 2 Hydrate temperatures are computed by created software and counter-checked industry-avail-
try-available software. able software.
3 Depression value is defined as system temperature (i.e., 287.2 K) minus hydrate temperature. 3 Depression value is defined as system temperature (i.e., 236.2 K) minus hydrate temperature.
4 Inhibitor flowrate based on 1 kg/h condensed H2O phase. 4 Inhibitor flowrate based on 1 kg/h condensed H2O phase.
5 Wt% indicates inhibitor purity used in inhibition package. 5 Wt% indicates inhibitor purity used in inhibition package.

TABLE 6A. Upstream inhibitor flowrate calculation TABLE 6B. Downstream inhibitor flowrate
at step 6 of EDPV depressurization process (P = 1.57 calculation at step 6 of EDPV depressurization process
bara) (P = 1.30 bara)
Inhibitor1 Hydrate2 Depression3 Flowrate,4 kg/h Inhibitor1 Hydrate2 Depression3 Flowrate,4 kg/h
wt% temp., K value, K 100%5 96%5 90%5 wt% temp., K value, K 100%5 96%5 90%5

30 213.0 50.3 30 210.3 48

40 207.4 44.7 0.11 0.12 0.13
40 204.9 42.6 0.11 0.12 0.13

50 200.8 38.1 0.25 0.26 0.29
50 198.4 36.1 0.25 0.26 0.29

60 193.0 30.3 0.43 0.45 0.50
60 190.7 28.4 0.43 0.45 0.50

70 183.8 21.1 0.67 0.71 0.80
70 181.8 19.5 0.67 0.71 0.80

80 172.7 10.0 1.00 1.09 1.25
80 171.0 8.7 1.00 1.09 1.25

90 156.5 6.2 1.50 1.67 2.00
90 155.5 6.8 1.50 1.67 2.00
1  eOH is selected as inhibitor in inhibition package. Also, wt% in this column shows inhibitor
M 1  eOH is selected as inhibitor in inhibition package. Also, wt% in this column shows inhibitor
M
wt% in the condensed liquid H2O phase in the pipeline. wt% in the condensed liquid H2O phase in the pipeline.
2 Hydrate temperatures are computed by created software and counter-checked by indus- 2 Hydrate temperatures are computed by created software and counter-checked by indus-
try-available software. try-available software.
3 Depression value is defined as system temperature (i.e., 162.7 K) minus hydrate temperature. 3 Depression value is defined as system temperature (i.e., 162.3 K) minus hydrate temperature.
4 Inhibitor flowrate based on 1 kg/h condensed H2O phase. 4 Inhibitor flowrate based on 1 kg/h condensed H2O phase.
5 Wt% indicates inhibitor purity used in inhibition package. 5 Wt% indicates inhibitor purity used in inhibition package.

Depressurization is required for both operational reasons and Blowdown temperature. For process equipment design,
emergency situations. During an emergency, it is used to rapidly minimum blowdown temperature should be determined. This
reduce pressure in the plant significantly below operating pres- identifies construction materials and also the required hydrate
sures. To facilitate a swift and controlled blowdown, the process inhibitor. Similar to determining blowdown rate, blowdown
plant is segregated by ESDVs into discrete sections. Each section temperatures are computed using a depressurization module in
has at least one emergency depressurizing point (Figs. 1 and 2). a process simulation program. It is used in the adiabatic mode,
Each system emergency depressurization is made possible via which simulates user blowdown, selected isentropic efficiency and
a dedicated emergency blowdown line connected to the plant heat transfer area. Upstream and downstream temperatures of the
flare network. In the blowdown line, a restriction orifice (RO) is relieved gas related to EDPVs and its composition are shown in
installed, across which pressure reduction is carried out. The RO Tables 3 and 4.
should be sized to achieve the required blowdown rate. The ESDV Hydrate formation. By using a calculation software package
is upstream of the RO and is equipped with on/off action and an and process simulation, hydrate formation temperatures at each
inhibitor injection package. depressurization process step can be obtained. Hydrate formation
conditions were calculated and reported in Table 3. Here saturated
Blowdown rates. These are calculated according to API RP hydrocarbon gas mixture with H2O is defaulted.
521, using a process simulation program depressurization mod-
ule.16, 17 This can be used in a fire case mode with a supersonic Package specification. Two main characteristics for any
valve, simulating blowdown under heat input from fire condi- hydrate inhibition package are:
tions. In this example, the depressurizing stream is modeled from Type
system operating pressure to system design pressure and heat input Flowrate.
at a constant system volume (i.e., constant stream density). Table Determining these two parameters must be done by P-T his-
2 shows these results. tory prediction and hydrate formation temperature.
Inhibitor type. Alcohol, glycols and their mixture can be used
HYDROCARBONPROCESSING APRIL 2006 5
I
PROCESS
H
= OPTIMIZATION
2063 (7) (7)
3 ln P nR 1 + 2 P + 3 ln P
aw,k = Activity of H2O in a binary solution containing H2O
as inhibitors in inhibition packages. Gas composition and pressure and electrolyte k with the same ionic strength as the
heavily influence effectiveness and cost. Comparing different mixture of all electrolytes and H2O
)
ln a w , k ln
media on a hydrate
a w =the
select (k most )
formation
mk ln ainhibitor.
mk suitable
w,k
temperature diagram can easily
(8)
Hydrate formation temperature
A = Constant in Eq. 6
b = Constant(8) in Eq. 3
B = Constant in Eq. 6
is a function of the inhibitors wt% coexisting in equilibrium with C = Langmuir constant, MPa
gas
H and hydrate 0 I 1phases. Figs. 3 and 4 are a comparison between
(9) Cp = H2O heat capacity, J/mol K
EG =and MeOH for hydrate formation in the example synthetic (9) MPa
f = Fugacity,
ln P nR 1 + P + ln P
0 1
gas mixture. For equal inhibitor weights, MeOH decreases hydrate h = Enthalpy of pure H2O, J/mol K
I = Ionic strength
formation temperature more than EG and, as a result, for this k = Boltzman constant, J/K molecule
specific example, it appears to be the more suitable inhibitor. mk = Molality of electrolyte k in the electrolyte solution,
+ ln a w , el ln aInhibitor flowrate. The injected inhibitor amount must
w , mix . = ln a w , al + ln a w , el
(10) be mol/1,000 g solvent
(10) of electrolyte k in an aqueous mixture containing
sufficient to prevent freezing the inhibitor H2O phase. There mk = Molality
only electrolyte k with the same ionic strength as the mixture,
must also be enough solution for the equilibrium vapor phase mol/1,000 g solvent
content of the inhibitor and its solubility in any liquid hydro- n = Hydrate number
H carbon. H H
MeOHs pressure is high enough that significant
vapor P = Pressure, MPa
2 will vaporize.
r = Separation distance between molecule cores,
R el Hamounts nR al nR el EG, diethylene glycol (DEG)(11) and TEG
= been used for hydrate inhibition. The most popular is EG Gas constant, 8.314 103
R = (11)
H have
nRduetoH H T = Temperature, K
R el its lower + cost, lower viscosity and lower solubility in liquid
nR
hydrocarbons. al nR el
Based on the material balance, inhibitor mass flowrate required
Babak Asadi Zeydabadi is a project manager in inter-
in the H2O phase is: national projects development affairs (IPDA) at Namvaran Man-
agement and Engineering firm, Tehran, Iran. He has been with
2 (12)
X = (12)
IPDA at NME since April 2004. Mr. Zeydabadi received his BS and
1 2 MS degrees in chemical engineering from Shiraz University. He
has worked as a senior process engineer for Petrochemical Industries Design and
Engineering Co. (PIDEC), a private engineering company based in Shiraz, Iran. Mr.
where: Zeydabadi cooperated with Oil Industries and Engineering Co. Group (OIEC) and
X is injected inhibitor mass flowrate based on 1 kg/h worked as senior process engineer at the Abadan oil refinery project for the National
Iranian Oil Engineering & Construction Co. (NIOEC) as well. He has published several
condensed H2O phase
technical papers in international journals and presented many technical papers at sci-
1 is inhibitor purity entific conferences. He can be reached via e-mail: b.asadizeydabadi@namvaran.com
2 is inhibitor weight fraction in the condensed H2O phase.
To select effective and suitable inhibitor flowrates, at each P-T
history step, inhibitor quantity can be calculated based on the Mahmood Moshfeghian is a senior research scientist at
above outlined procedure. Tables 5 and 6 show typical inhibitor Petroleum Research and Studies Center (PRSC), Kuwait Institute for
Scientific Research (KISR). His research fields are thermodynamics
flowrates at steps 1 and 6 of the depressurizing process related applications in the oil and gas industries, equation of state, res-
to EDPV. The inhibitor flowrate extracted from Tables 5 and 6 ervoir PVT and phase behavior, gas conditioning and processing,
should be doubled to compensate for losses to the hydrocarbon natural gas transportation, process flow simulation, and software development. He
liquid phase and vaporization. has a BS, MS and PhD in chemical engineering from Oklahoma State University. Dr.
Moshfeghian was a professor of chemical engineering at the University of Qatar and
University of Shiraz before joining KISR. He has taught courses in BS, MS and PhD
Using the method. Hydrate formation must be considered by levels for 25 years. He has supervised more than 20 MS theses and 4 PhD dissertations
many HPI facilities as it can impose serious and crucial operating and has been an external examiner for more than 10 PhD dissertations worldwide.
hazards. Using inhibitors such as alcohol and glycols prevent Dr. Moshfeghian has published more than 90 papers in international journals and
has presented more than 70 technical papers at scientific conferences. He has also
formation effectively and economically. authored and co-authored several chemical engineering software programs such as
A methodology for selection and sizing inhibition packages is a GCAP, and EzThermo.
useful tool in HPI facilities. The chosen emergency depressuriza-
tion valve is responsible for rapid and safe system depressurization.
Shahram Roshani is a senior process engineer in the process
System P-T history should therefore be known before and after engineering dept. (PED) at Petrochemical Industries Design and
the pressure reduction valve. Having established this information, Engineering Co. (PIDEC), Shiraz, Iran, which he joined in 1994. Dr.
hydrate formation temperature at each depressurization step can Roshani received his BS and PhD degrees in chemical engineering
then be computed using calculations and simulation software from Teesside Polytechnic and Leeds Universities, respectively. He
has been responsible for basic and detailed engineering designs for various petro-
packages. chemical plants in Iran. Dr. Roshani has authored articles on heat transfer and reactor
A suitable inhibitor can then be selected by comparing differ- design and can be contacted by e-mail: roshani-sh@pidec.com
ent media on a hydrate formation temperature diagram. Based
on the material balance the mass flowrate of the chosen inhibitor
is computed by using Eq. 12. Having established the inhibitor Mehri Haghshenas is a senior process engineer in the pro-
cess and chemical engineering dept. at Namvaran Management
type and flowrate, the entire inhibition package can then be accu- and Engineering firm, Tehran, Iran, which she joined in April 2004.
rately and reliably sized, thus improving facility operations and She received her BS degree in chemical engineering from Shiraz
economics. HP University. Ms. Haghshenas has also worked as a senior process
engineer for Petrochemical Industries Design and Engineering Co. (PIDEC). In 2001,
she cooperated with Oil Industries and Engineering Co. Group (OIEC) and after that
NOMENCLATURE
worked as senior process engineer for the Abadan oil refinery project in the client
a = Constant in Eq. 3 groups at the National Iranian Oil Engineering & Construction Co. (NIOEC). Ms.
aw = Activity of H2O Haghshenas can be reached via email: m.haghshenas@namvaran.com

6
I APRIL 2006 HYDROCARBONPROCESSING
PROCESS OPTIMIZATION
x = Mole fraction in liquid H2O phase LITERATURE CITED
X = Inhibitor mass flowrate provided by inhibition package 1  oshfeghian, M. and R. N. Maddox, Method predicts hydrates for high
M
based on one kg/h condensed H2O phase, kg/h pressure gas streams, Oil & Gas Journal, pp. 7881, 1993.
2 Ripmeester, J. A., J. S. Tse, C. I. Ratcliffe and B. M. Powell, A new clathrate

GREEK LETTERS hydrate structure, Nature, 325, 135, 1987.


3 Mehta, P. A. and E. D. Sloan, A thermodynamic model for structure-H
a0, a1 = Constants in Eq. 9
b0, b1 = Constants in Eq. 9 hydrates, AIChE Journal, Vol. 40, pp. 312320, February 1994.
4 Engineering Data Book, 10th edition, GPSA, Tulsa, Oklahoma, 1994.
1, 2,, 3 = Constants in Eq. 7 5 Campbell, J. M., Gas Conditioning and Processing, Vol. 2, Campbell Petroleum
= Molar volume, m3/mol
1 = Inhibitor purity used in inhibition package Series, Norman, Oklahoma, 1994.
6 Nasrifar, K., M. Moshfeghian and R. N. Maddox, Prediction of equilibrium
2 = Inhibitor weight fraction in the condensed H2O phase
= Chemical potential, J/mol conditions for gas hydrate formation in the mixtures of both electrolytes and
D = Indicates difference in thermodynamic property value alcohol, Fluid Phase Equilibria Journal, pp. 113, 1998.
7 Moshfeghian, M., R. N. Maddox, EZ-Thermo Software, Chemical Engineering
of H2O in two phases
= Cell potential, J/molecule Consultants, Stillwater, Oklahoma, 1996.
8 Parrish, W. R. and J. M. Prausnitz, Dissociation pressures of gas hydrates formed

by gas mixtures, Ind. Eng. Chem. Process Des. Dev. 11, pp. 2635, 1972.
SUPERSCRIPT 9 Valderrama, J. O. and J. Chemical Engineering Journal, pp. 8791, 1990.
= Reference state 10 Pieroen, A. P., Recueil Trav. Chim. Vol. 74, 1955.
11 Javanmardi, J. and M. Moshfeghian, Proceedings of the 2nd International
SUBSCRIPTS Conference on Natural Gas Hydrate, pp. 101108, June 1996.
12 Patwarthan, V. S. and A. Kumar, AIChE Journal, Vol. 32, pp. 14191428,
al = Alcohol
1986.
el = Electrolyte 13 
i, j = Indicate gas species Pitzer, K. S. and G. Mayorga, Journal of Physical Chemistry, Vol. 77, pp.
mix = Mixture 2,3002,308, 1973.
14 Javanmardi, J., M. Moshfeghian and R. N. Maddox, Simple method for
o = Indicates hydrate temperature in the presence of pure H2O
predicting gas-hydrate-forming conditions in aqueous mixed-electrolyte solu-
R = Reference state
tions, The Journal of Energy and Fuels, Vol. 12, pp. 219222, 1998.
w = H2O phase 15 Gruhn, P. and H. L. Cheddie, Safety Shutdown Systems: Design, Analysis and

Justification, ISA Publications, 1998.


ACKNOWLEDGEMENT 16 Guide for pressure-relieving and depressuring systems, API/RP, 521, 4th
The authors wish to express their gratitude to the management of National Edition, 1998.
Iranian Oil Co. (NIOC) for its support and assistance in this study. The authors 17 PRO/II Manual, Version 3.3, Sim. Sci. Inc., October, 1992.

also appreciate the computer and laboratory facilities provided by the Petrochemi- 18 Nasrifar, K., M. Moshfeghian, A. H. Johannes and R. N. Maddox, Predict

cal Industries Design & Engineering Co. (PIDEC) and Oil Industries Engineering gas hydrate-forming temperature, Hydrocarbon Processing, pp. 7780, April
& Construction Co. (OIEC). 1999.

Eprinted and posted with permission to Shell Global Solutions from Hydrocarbon Processing
Including consent to make single copies for distribution
April 2006 Gulf Publishing Company

HYDROCARBONPROCESSING APRIL 2006 7


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